N-hydrocarbyloxyiminomalononitriles and process for preparing them



United States Patent 3,234,266 N-HYDROCARBYLOXYIMINOMALONONITRILES ANDPROQIESS FOR PREPARING THEM Elwood P. Blanchard, In, Wilmington, Dei.,assignor to E. L du Pont de Nemours and Company, Wilmington,

Del., a corporation of Delaware No Drawing. Filed Aug. 13, 1963, Ser. N301,909 6 Claims. (Cl. 26tl465.5)

This invention is concerned with a new class of organic chemicalcompounds and a process for their preparation. More particularly, it isconcerned with substituted iminomalononitriles and closely relatedcompounds.

The compounds of this invention are N-hydrocarbyloxyiminomalononitriles.They are prepared by the reaction of an alkali or alkaline earth metalsalt of isonitrosomalononitrile with a hydrocarbyl halide or sulfate.This may be illustrated by the equation:

where M is one equivalent of an alkali or alkaline earth metal ion, R isa hydrocarbyl group of 20 carbon atoms or less, and X is a halogen,i.e., F, Cl, Br, or I or a sulfate group, OSO OR. Metals preferred for Mare the alkali metals, i.e., lithium, sodium, potassium, rubidium, andcesium.

Hydrocarbyl is used in its accepted meaning as representing a monovalentradical formed from a hydrocarbon by removal of a hydrogen atom. Thehydrocarbyl groups represented by R in Formulas II, III, IV, VI, VII,and IX may be any radical composed solely of carbon and hydrogen andcontaining 20 or fewer carbon atoms. Hydrocarbyl is used in its fullgeneric sense. The wide variation in the hydrocarbyl groups used in theillustrations which follow makes it evident that all such hydrocarbylgroups are operable. Hydrocarbyl groups may vary as to whether they arealkyl, cycloalkyl, aryl, aralkyl, alkaryl, single ring, multi ring,aliphatically saturated, aliphatically unsaturated, straight chain,branched chain, large, small, and the like. The widest variation of thissort does not in any way detract from the fundamental characteristic ofthe hydrocarbyl radical of passing unchanged through the process of thisinvention and exercising no effect whatever on the chemical steps of theprocess. Representative hydrocarbyl groups include alkyl groups such asmethyl, ethyl, tert-butyl, hexyl, isooctyl, dodecyl, octadecyl, eicosyl,alkenyl and alkynyl groups such as vinyl, ethynyl, propargyl,Q-octadecenyl, 9-octadecynyl,

butadienyl, 9,l2octadecadienyl; cycloalkyl groups such as cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, carnphyl,methylcyclohexyl, 3,5-dicyclohexylcyclohexyl, cyclooctadecyl,cycloeicosyl; aryl groups such as phenyl, naphthyl, anthryl,p-biphenylyl, p,p'-triphenylyl, naphthacenyl, benzanthryl, chrysenyl,9-phenyl-l-anthryl; alkaryl groups such as p-tolyl, duryl, p-cumenyl,p-vinylphenyl, 2,4,6-tributylphenyl, 4-isopropylnaphthyl,9,10-diethyl-l-anthryl, 9-hexyl-1-anthryl, 6-methyl-2 naphthyl; andaralkyl groups such as benzyl, phenethyl, styryl, diphenylmethyl,triphenylmethyl, a,,8,;3-triphenylethyl, naphthylethyl,2-(2-anthryl)ethyl, 4-(2-anthryl) butyl, and the like.

It is obvious that hydrocarbyl groups containing 12 or fewer carbonatoms, particularly those containing 6 or fewer carbon atoms, are leastexpensive and most available, and to that extent preferred. But there isto be no question of the operability of, or of the intent to include anddisclose, any hydrocarbyl group whatsoever containing 20 or fewer carbonatoms. In this connection also, the preferred hydrocarbyl groups arefree of acetylenic type carbon-to-carbon unsaturation, and, morepreferred yet, are those hydrocarbyl groups entirely free of aliphaticPatented Feb. 8, 1966 carbon-to-carbon unsaturation, i.e., those whichare allphatically saturated.

Hydrocarbylidene is used to designate a radical otherwise similar tohydrocarbyl as defined above except that it is divalent and both bondsstem from the same carbon atom.

The reaction of an alkali or alkaline earth metal salt ofisonitrosomalononitrile with a hydrocarbyl halide or sulfate to obtainan N-hydrocarbyloxyliminomalononitrile may be carried out without thepresence of any added materials. Thus, the reaction can be carried outby impact grinding the reactants together in a closed container;however, it is preferred to carry out the reaction in the presence of aliquid reaction medium which is inert to the reactants and products.Suitable liquids include water; alcohols such as methanol, ethanol,butanol, and hexanol; ethers such as dimethyl ether, diethyl ether, andtetrahydrofuran; hydrocarbons such as hexane, petroleum ether, benzene,and toluene, and the like, as Well as mixtures of the above namedliquids.

Pressure is not a critical factor in this reaction, and pressures in therange from 0.1 to atmospheres and above are operable. Atmosphericpressure is preferred for convenience. The reaction may be carried outat temperatures in the range 0-200 C.

The molar ratio in which the reactants are brought together to carry outthis reaction is also not critical. Molar ratios from 1:19 to 19:1 maybe employed. Molar ratios of about 1 :1 are the most practical.

The N-hydrocarbyloxyiminomalononitriles of the invention react readilywith hydrazine to form 2-cyano-2- (hydrocarbyloxyimino)acetamidehydrazones as indicated by the equation:

The 2-cyano-2-(hydrocarbyloxyimino)acetamide hydrazones in turn reactreadily with monocarbonyl compounds such as aldehydes and ketones toyield the corresponding Z-cyano-Z (hydrocarbyloxyimino)acetamidehydrocarbylidenehydrazones as the principal product and a-(hydrocarbyloxyimino)-A -l,2,4-triaZoline-3 acetonitriles as minorproducts as shown, respectively, in the following equations:

(VII) in which R is as defined above, R is defined the same as R, and Rmay be hydrogen or R with the additional proviso that R and R", takentogether, may represent a polymethylene chain of 2-7 members, i.e., (CHwhere n is from 2-7 inclusive.

The Z-cyano 2 \(hydrocarbyloxyimino)acetamide hydrazones also reactreadily with vicinal dicarbonyl compounds such as vicinal diketones andvicinal ketoaldehydes such as methylglyoxal to yield the correspondinga-(hydrocarbyloxyimino)-l,24-triazine-3-acetonitriles as shown in thefollowing equation:

in which R, R, and R are as defined above.

Cyclic embodiments of compounds of Formulas V and VIII which may beemployed in the processes described above include cyclopropanone,cyclohexanone, cyclooctanone, 1.,2-cyclobutanedione,1,2-cyclopentanedione, -1,2-cycloheptanedi-one, and the like.

In the reaction of compounds of Formula III with hydrazine as well asthe reactions of compounds of Formula IV with compounds of Formulas Vand VIII, as shown in the equations above, the process conditions,including the effect of a liquid reaction medium, pressure, temperature,and molar ratio ranges, arethe same as those defined above with thesingle exception that in these latter pr-ocesses'it is preferred thatthe temperature of the reaction be in the range from to 100 C.

In the following examples parts are by weight unless otherwiseindicated. Example H represents a preferred embodiment.

Example I To a solution of 1330 parts of potassiumisonitrosomalononitrile in a mixture of 10,000 parts of water and 3947parts of ethanol is added with stirring 1260 parts of methyl sulfate. Anexothermic reaction occurs accompanied by the formation of a deep redcolor. The mixture is allowed to stand for 48 hours, and then thevolatile material is distilled at reduced pressure. The distillate isextracted with ether, the ether phase dried over MgSO filtered, and theether distilled. The two-phase residue is separated and the upper phaseeluted from a short column of alumina (Activity I) with 1784 parts ofether. The eluate is concentrated and the residue distilled to give 114parts of N-methoxyiminomalononitrile.

Analysis.-Calcd. for C H N O: C, 44.00; H, 2.75; N, 38.5. Found: C,44.81; H, 3.13; N, 38.00.

Example II To a stirred solution of 266 parts of potassiumisonitrosomalononitrile in 873 parts of ethylene glycol dimethyl etheris added 300 parts of methyl iodide. An exothermic reaction ensues.After one hour the mixture is cooled and passed through a short columnof Activity I alumina and eluted with 5600 parts of ether. The eluate ispassed through a second column of Activity I alumina and then the eluateis concentrated by distillation. Fractionation of the residue gives -65parts of N-methoxyiminomalononitrile in the form of a colorless liquid,B.P. 88-90 C. at 105 mm. Hg and 11 1.4431. When methyl bromide issubstituted for methyl iodide in the procedure of this example,N-methoxyiminomalononitrile is also obtained.

Example III To a solution of 32 parts of anhydrous hydrazine in 789parts of alcohol is added a solution of 109 parts ofN-methoxyiminomalononitrile in 789 parts of alcohol. An immediateexothermic reaction occurs with formation of a yellow crystallineprecipate. After 1.5 hours the mixture is cooled to 0 C., filtered, andthe crystals dried in a CaCl desiccator to leave parts of 2-cyano-2-(methoxyimino)acetarnide hydrazone in the form of pale yellow plates,M.P. C. (dec.).

Analysis.Calcd. for C4H'1N50: C, 34.02; H, 4.95; N, 49.60. Found: C,34.47, 34.58; H, 5.06, 5.03; N, 49.29, 49.70.

Example IV Two hundred parts of 2cyano-2-(methoxyimino)- acetamidehydrazone and 344 parts of benzil are dissolved in 2368 parts of ethanolby warming on the steam bath. After standing 15 hours at roomtemperature, the mixture is cooled to 0 C. and the crystals filtered.The filtrate is concentrated at reduced pressure and the crystallineresidue combined with the residue from the filtration. Recrystallizationfrom ethanol gives 346 parts of a-(methoxyimino) 5,6diphenyl-1,2,4-triazine-3- acetonitrile as yellow needles, M.P. 165167C.

Analysis.Calcd. :for C H N Ot C, 68.55; H, 4.13; N, 22.20. Found: C,68.13, 68.20; H, 3.91, 4.07; N, 23.07, 23.02.

Example V To a solution of 141 parts. of2-cyano-2.(methoxyimino)acetamide hydrazone in 1600 parts of hot ethanolis added 90 parts of 2,3-butanedione and the solution heated at refluxfor five minutes. On cooling, crystals deposit and are collected byfiltration. Recrystallization from alcohol gives 70 parts ofa-(methoxyimino)5,6 dimethyl-l,2,4-triazine-3-acetonitrile, M.P. 143 C.

Analysis.Calcd. for C H N O: C, 50.3; H, 4.7; N,

36.6. Found: C, 50.8; H, 5.0; N, 37.0.

Example VI A solution of 19 parts of 2-cyano-2-(rnethoxyimino) acetamidehydrazone in 40 parts of alcohol is treated with 15 parts of acetone andheated on a steam bath. Evaporation of the solvent leaves an oil whichis eluted from an alumina column with ethyl acetate and thenrecrystallized from hexane to give 13 parts of2-cyano-2-(methoxyimino)acetamide isopropylidenehydrazone, M.P. 70- 71C.

Analysis.-Calcd. for C H N O: C, 46.4; H, 6.1; N, 38.6. Found: C, 47.2;H, 6.2; N, 39.9.

Example VIII A solution of 107 parts of 2-cyano-2-(methoxyimino)acetamide hydrazone in 1600 parts of 1,2-dimethoxyethane is treated with100 parts of cyclohexanoneand allowed to stand for six hours. Thesolvent is evaporated and the residual oil eluted from an alumina columnwith ether. Evaporation of the ether eluate and recrystallization fromether-petroleum ether gives 100 parts of 2- cyano 2 (methoxyimino)acetamide cyclohexylidenehydrazone, M.P. 69-71 C.

Analysis.Calculated for C H N O: C, 54.3; H, 6.8; N, 31.6. Found: C,54.1; H, 6.8; N, 32.5.

Example [X To a solution of 90 parts of 2-cyano-2-(methoxyimino)acetamide hydrazone in 2000 parts of alcohol is added 15 parts ofconcentrated hydrochloric acid and 100 parts of acetophenone. Themixture is warmed on the steam bath and then allowed to stand 0.5 hour.Addition of 10,000 parts of water results in the precipitation of yellowcrystals. The crystals are collected and recrystallized from aqueousethanol to give 115 parts of Z-cyano-Z- (methoxyimin)acetamide amethylbenzylidenehydra- 6 Example XI To-a boiling solution of 2 parts ofZ-cyano-IZ-(methoxyimino)acetamide benzylidenehydrazone and 2 parts of asulfonated 1i in dis ersant in 20 000 arts of water are zone, M.P.95.5-96.3" 0. f p p A l c I d f C H N C 59 H 5 3? added swatc es offabrics of polyacrylonitrrle, 66 nylon, N 5 2;-

g P silk and Wool. Boiling is continued for one hour. The

mm 'fi I y swatches are removed from the dye bath, rinsed with 1 e 9? iecuhar $3 d y f y i f water, washed with soap and Water and again rinsedwith ma (mom n e W cm e y groups col} am Water. The dried fabrics areall dyed a golden tan.

1-8 carbon atoms) are colorless liquids and, as illustrated in ExampleX, are useful as solvents for preparing Example XII i u i t films ofpolymenc matfl als 5 Ch as polyv nyl aceta 6 Tea solution of two partsof a-(methoxyirn1no)-5,6-di- Example Xphenyl-l,2,4-triazine-3-acet-onitrile and two parts of a sul- Five partsof granular high viscosity polyvinyl acetate fonated lignin dispersantin 20,000 parts of water heated is stirred at room temperature intoabout 100 parts of N- at about 100 C. are added swatches of fabrics of66 methoxyiminomalononitrile to obtain a clear, viscous sonylon, silk,and wool. Heating and stirring are continued lution. This solution isspread on a glass plate and the for one hour. The swatches are thenremoved from the N-rnethoxyiminornalononitrile is allowed to evaporate.dye bath, rinsed with water, washed with soap and water, The resultingfilm of polyvinyl acetate is stripped from and again rinsed with water.The dried fabrics are all the plate and found to be clear, tough andflexible. dyed tan in color.

The higher molecular Weight N-hydrocarbyloxyimino- When the halides (A)indicated in Table I are substimalononitrile (i.e., Where thehydrocarbyl groups contain tuted for methyl iodide in the procedure ofExample II, 8-20 carbon atoms) are viscous liquids, greases and waxy theindicated N-hydrocarbyloxyiminomalononitriles (B) solids. Thesecompounds are sufiiciently non-volatile at are obtained. These productsare treated with hydrazine atmospheric pressure to be useful asnon-migrating plasaccording to the procedure of Example III to obtainthe ticizers for polyvinyl acetate, polyvinyl chloride andsiniiindicated 2-cyano-2-(hydrocarbyloxyiniino)acetamide hy- Iar vinylpolymers. drazones (C). These hydrazones react with the indicated The2-cyano-2-(hydrocarbyloxyimino) acetamide hymonoca'rbonyl compounds (D)according to the procedrazones of Formula IV, the2-cyano-2-(hydrocarbyloxydure of Example VI to yield the indicatedZ-cyano-Z- imino)acetarnide hydrocarbylidenehydrazones of For-(hydrocarbyloxyimino)acetarnide hydrocarbylidenehydramula VI, and thea-(hydrocarbyloxyimino)-1,2,4,-triazinezones (E) and with the indicatedvicinal dicarbonyl com- 3-acetonitriles of Formula IX are all coloredcompounds pounds (F) according to the procedure of Example V to and allare useful as dyes for fabrics. This is illustrated in to yield theindicated OL-(hYdI'OCRIbYIOXYlIIIiHO)-1,2,4t1'l- Examples XI and XII.azine-3-acetonitrile (G).

TABLE I Item A. Halide B. N-Hydrocarbyloxyimino- C2-Oyano-2-(hydrocarbyloxy- D. Monocarbonyl Compound malononitrile1mino)acetamide hydrazone 1 Ethyl brnmidP N-ethoxyiminomalononitrile. 2-i1yaio-2(ethoxyamino)acetamide Stearophenone.

y razoner 2 t-Butylchloride N-t-butoxyiminomalononitrile- 2i1yadr}0-2-(t-butoxyimino)acetzunide Methyl vinylketone.

y azOne. 3 n-Octyl bromide N-octyloxyimiuomalononitri1e.2-rgra510-2-(cctyloxyimino)acetamide Di-n-octylketone.

y razone. 4 n-Dodecyl bromide N-d0decycloxyirninomalononi-2-cyano-2-(dcdecyloxyirnino) Methylethynyl ketone.

trile. acetamide hydrazone. 5 n-OctadecyliodideN-Octadecyloxyirninoinalononi- 2-cyano-2-(octadeeyloxyimino) Stearone,

trile. acetamide hydrazone. 6 n-EieosylbronlideN-eic0syl0xyiminomalononi- 2-cyanc-2-(eicosyloxyimino) Methylcyelohexylketone,

trile. acetamide hydrazone 7 Cyclopropyl chlorideN-cyclopropyloxyirninomalono- 2-cyano-2-(cyclopropyloxyimino) Di-n-butylketone.

nitrile. acetamide hydra-zone. 8 Cyclopropylmethyl bromideN-cyclopropylmethoxyimino- 2-cyano-2-(eyclopropylmethoxy Ethyl t-bntylketone.

malononitrile. imino)acetamide hydrazone. 9 Cyclobutyl bromideN-cyclobutoxyiminomalono- 2-cyan0-2-(cyclobutoxyimino) Propargylaldehyde.

nitrile. acetamide hydrazone. 10 Cyclopentyl iodideN-cyclopentyloxyiminoma- Z-cyano-Z-(cyclopentyloxyimino)3,4-benzpyrene-6-aldehyde,

lononitrile. aeetamide hydrazonei 11 CyclohexyliluorideN-cyclohexyloxyiminoma- 2-cyan0-2-(cyclohexyloxyimino) Q-anthraldehyde.

lononitrile. acetamide hydrazone. 12 Cyclooctyl bromideN-cyclooctyloxyirninoma- 2-cyan0-2-(cyclocctyloxyimino)B-Naphtthaldehyde,

lononitrile. acetamide hydrazone. 13 Vinyl fluorideN-vinyloxyiminomalononitrileee 2-ckyalo-2-(vinyloxyimino)acetamideOctndccanal.

y razone. 14 Iodobeuzene N-phenoxyiminomalononitrile.2-gyairo-2-(phenoxyimino)acetamide DodecanaL y azone. 15 AllyliodideN-allyioxyiminomalouonitrile-. 2-chyaio-2-(allyloxyimino)acetamiden-Octylaldchyde.

y razone. 16 p-Brornobiphenyl N-p-biplienylyloxyiminoma-2-cyan0-2(p-biphenylyloxyimino) Butyraldehyde.

lononitrile. acetamide. 17 2-ch1oro-1,3-butadieneN-(1,3-butadieue-Lyl)oxyimi- 2-cya110-2-(1,B-butadiene-Z-yl-oxy-Acetaldehyde.

nomalononitrilc. imino)acetarnide hydrazone. 18 wChloronnphthaleneN-wnaphthyloxyimiuomalono- 2-cyano-2-(a-naphthyloxyimino) Acetone.

nitrile. acetamicle hydrazone. 19 1-chlorocyclohexeneN-l-cyclohexenyloxyimino- 2-cyano-2-(Lcyclohexenyloxyimino) Methyl ethylketone.

malononitrile. aeetamide hydrazone. 20 l-iodophenanthreneN-phenanthryloxyiminomala 2cyan0-2-(phenanthryloxyimino)Propionaldehyde.

nonitrile. acetamide hydrazone. 21 fi-ChlorostyreneNetyryloxyimiuommononitrila. 2-cyanc 2-(styryloxyimino)-aceta-Isobutyraldehyde.

mide hydrazone. 22 i-phenylbutyl chloride N-4phenylbutoxyiminornalo-2-cyano 2 (4-phenylhutoxyimino) Butyrophenone.

nonitrile. acetarnide hydrazone. 23 Triphenylvinyl bromideN-triphenylvinyloxyiminoma- 2-cyano-2-(triphenylvinyloxyimino) Dipropylketone.

lononitrile. acetarnide hydrazone. Qbromonnthracene N-anthryloxyiminomalono- 2-cyan0-2-(Qanthryloxyimino) Acetone.

nitrile. acetamide hydrazone. l-ehloro-LoctyneN-1-0ctynyl0xyiminomalon0- 2-cyan0-2-(Loctynyloxyimino) Butyraldehyde.

nitrite. acetamide hydrazone. 26 Benzyl fluoride N-benzyloxyiminomalonm2cyano2-(benzyloxyimino)-aceta- Benzaldehyde.

nitrile. mirle hydrazone. 27 TriphenylchloromethaneN-t-riphenylmethoxyiminoma- 2-cyano-2-(triphenylmethoxyimino) Acetone.

lononitrile. acetamide hydrazone.

Item E. 2-Cyan0-2-(hydroearbyloxyimino)acetamide F. Vicinal DicarbonylG. a-(Hydrocarbyloxyimino)-1,2,4-tIiazine-3- HydrocarbylidenehydrazoneCompound acetonitrile 1 2-eyano2(eth0xyimino) aeetamide a-heptadecyl-4-methylbenzil a-ethoxyimino- (6)-phenyl-6(5)-p-t01y1-1,2,4-

benzylidenehydrazone. triazine-B-acetonitrile. 22rcyano-2-(t-bntoxyimino)acetamide a-vinylethylp-Tolila-(t-butoxyimino)-5,G-di-p-tolyl-1,2,4triazi11eidenehydrazone.3-acetonitrile. 3 2-cyano-2-(octyloxyimino) acetamidea-octylnonyll-phenyl-l,2-butaned1one a-octyloxyimino-5(6)-ethyl-6(5)-phenyl-1,2,4-

idenehydrazone. triazine-3-acetonitrile. 42-eyano-2-(dodecyloxyimino)acetamide a-ethynyl- Acetylbenzoyla-dodecyloxyimino-5(6)methyl-6 (5) -pheny1- ethylidenehydrazone.1,2,4-triazine-3-acetonitri1e. 5 2-cyan0-2-(oetadeeyloxyimino)acetamidea-hepta 1,2-0y010h0ptan9d10newontadecyloxyimino-5,G-pentamethylene-l,2,4-

decyloctadeeylidenehydrazone. triazine-3-acetonitrile. 62-eyan0-2-(eicosyloxyimino)acetamide a-cyclohexyld0a-eic0sy10xyimino-5,6-trimethy1ene-1,2,4-

ethylidenehydrazone. triazine-3-acetonitrile.2-cyano-2-(cyclopropyloxyimino) acetamide a-butyl- Dnsobutyryla-cyclopropyloxyimino-5,G-diisopropyl-l,2,4-

pentylidenehydrazone. 2-cyano-2-(cyclopropylmethoxyimino)acetamidea-t-butylpropylidenehydrazone.

phenylbutylidenehydrazone. 4 Z-cyano-Z-(triphenylvinyloxyimino)aeetamide apropylbutylidenehydrazone.

propylidenehydrazone.

1,2-eyclohexanidione 1,2-cyclohexanedi0ne triazine-3-acetonitrile.a-cyelopropylmethoxyimino-5,fi-tetramethylene-1,2,4-triazine-3-acetonitrile 2-cyano-2-(cyclobutoxyimino)acetamidepropargyl- Dipivaloyla-Cy0l0but0Xyimin0-5,G-(t-butyl)-1,2,4-triazineidenehydrazone.3-acetonitrile. 2-cyan0-2-(cyclopentyloxyimino)acetamide (3,4-Dipropionyla-cyclopentyloxyimino-5,6-diethyl-1,2,4-tribenzpyrene-El-yl)methylidenehydrazone.I azine-3-acetonitrile. 2-cyano-2-(cyclohexyloxyimino)acetamideQ-anthryL! Benzllcr-cyc10hexyl0xyimin0-5,6-diphenyl-1,2,4-trimethylidenehydrazone.azine-3-acetonitrile. 2-cyano-2-(cyclooctyloxyimino)acetamide B-naphd0a-cyclooctyloxyimino-5,6-diphenyl-1,2,4trithylmethylidenehydrazone.azine-B-acetonitrile. 2-cyano-2(vinyloxyimino)-acetamide 0etadecy1iDmeetyl a-viny10xyirnino-5,6-dimethyl-1,2,4-triazinedenehydrazone.3-acetonitrile, 2-cyano-2-(phenoxyimino) acetamide dodecylidenedOa-phenoxyimino-5,G-dimethyl-l,2,4-triazinehydrazone. 3-acetonitr1le.2-cyano-2-(allyloxyimin0) acetamide octylidene- .(10a-allyloxyimino-S,6-dimethyl-1,2,4-triazinehydrazone. 3-acetonitrile.2-cyano-2-(p-biphenylyloxyimino) aeetamide butyle za-(p-biphenylyloxyimino)-5,6-dipheny1-1,2,4-

idenehydrazone. triazine-3-acet0nitri1e.2-cyano-2-(1,3-butadiene-Z-yloxyimino) acetamide .d0o:-(l,3-butadien-2-yloxyimir1o)-5,6-diphenylethylidenehydrazone.1,2,4-triazine-3-acetonitrile. 2-cyan0-2-(cz-naphthyloxyimino) acetamidelsopro- Diacetylu-(a-naphthyloxyimino)-5,6-dimethy1-1,2,4-tripylidenehydrazone.azine-3-acetonitrile. 2-cyano-2-(l-eyelohexenyloxyimino) acetamide a-.....do u-(l-cyclohexenyloxyimino)-5,6-dimethyl-1,2,4-

ethylethylidenehydrazone. triazine-3-acetonitrile.2-eyano-2-(phenanthryloxyimino)acetamide pr0- Benzlla-phenanthryloxyimino5,6-diphenyl-1,2,4-tripylidenehydrazone.azine-3-acetonitrile. 2-cyan0-2(styryloxyimino) acetamide B,B,-d1med0wstyryloxyimino-5,6-dipl1enyl-1,2,4-triazine-3- thylethylidenehydrazone.aeetonitrile. 2-eyano-3-(4-phenylbutoxyimin0)acetamide a- Dlacetyla-(4-phenylbutoxyimino)-5,6-dimethyl-1,2,4-triazine-3-acetonitr1le.a-triphenylvinyloxyimino-fi,Gtetramethylene-1,2,4-triazine-B-acetonitrile.

2-cyano-2-(9-anthryl0xyimin0) acetamide isopro- Benzlla-(Q-anthryloxyimino)-5,6-diphenyl-1,2,4-tri pylidenehydrazone.azine-3-acet0nitrile. 2-eyan0-2-(Loctynyloxyimino) acetamide butyl-Dlacetyl a(l-octynyloxyimino)-5,6-dimethyl-1,2,4-triidenehydrazone.azine3-acetonitrile. 2-cyano-2-(benzyloxyimino) aeetamide benzyli-Benzll a-ben zyloxyimino-5,G-diphenyl-l,2,4-triazine-3- denehydrazone.acetonitrile. 2-cyano-2-(triphenylmethoxyimino)aeetamide 1S0- Dlacetyloz-triphenylmeth0Xyimino-5,6-dimethyl-1,2,4-

triazine-3-acet0nitrile.

As many widely different embodiments of this invention may be madewithout departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula (3N R-O-N=CCN wherein R is a hydrocarbylgroup of 1 to carbon atoms.

2. A compound of the formula CN RON=( JCN where R is an alkyl group of 1to 12 carbon atoms.

3. A compound of the formula (1N Ro-N=o-0N where R is an alkyl group of1 to 6 carbon atoms.

4. N-methoxyiminomalononitrile.

5. Process for preparing an N-hydrocarbyloxyrminomalononitrile havingthe formula wherein R is a hydrocarbyl group of l to 20 carbon atoms,which comprises (I) contacting and reacting, at a temperature in therange 0 C. to 200 C. and a pressure in the range 0.1 atm. to atm., ametal salt of isonitrosomalononitrile wherein said metal is selectedfrom the class consisting of alkali metals and alkaline earth metalswith a compound RX wherein R is defined as above and X is selected fromthe group consisting of halogen and sulfate OSO OR wherein R is definedas above, with the molar ratio of said metal salt to RX being in therange 1:19 to 19:1, and (II) recovering saidN-hydrocarbyloxyiminomalononitrile.

6. The process of claim 5 wherein R is alkyl of 1 to 12 carbon atomswhich comprises (I) contacting and reacting, in the presence of a liquidreaction medium inert to the reactants and reaction products, an alkalimetal salt of isonitrosomalononitrile with an alkyl halide of 1 to 12carbon atoms, with the molar ratio of said metal salt to alkyl halidebeing about 1:1, and (II) recovering saidN-hydrocarbyloxyiminomalononitrile.

References Cited by the Examiner UNITED STATES PATENTS CHARLES B.PARKER, Primary Examiner.

1. A COMPOUND OF THE FORMULA